CN106832916A - High heat conductive insulating copolyamide composite and preparation method thereof - Google Patents
High heat conductive insulating copolyamide composite and preparation method thereof Download PDFInfo
- Publication number
- CN106832916A CN106832916A CN201710014341.8A CN201710014341A CN106832916A CN 106832916 A CN106832916 A CN 106832916A CN 201710014341 A CN201710014341 A CN 201710014341A CN 106832916 A CN106832916 A CN 106832916A
- Authority
- CN
- China
- Prior art keywords
- area
- temperature
- copolyamide
- resin
- heat conductive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC(C)(CCNC(C1CC(C(NC**)=O)=CCC1)=O)C(C)(C)OC(*)=* Chemical compound CC(C)(CCNC(C1CC(C(NC**)=O)=CCC1)=O)C(C)(C)OC(*)=* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Polyamides (AREA)
Abstract
The present invention relates to a kind of high heat conductive insulating copolyamide composite and preparation method thereof, the high heat conductive insulating copolyamide composite is prepared from the following materials：Copolyamide resin, aliphatic polyamide resin, toluene di-isocyanate(TDI), 2,2'(1,3 phenylenes) bisoxazoline, coupling agent, boron nitride, aluminum oxide, carborundum, N, N' double (2, the piperidyl of 2,6,6 tetramethyl 4) 1,3 benzenedicarboxamides and double (aminomethyl phenyl of 2,6 di-t-butyl 4) pentaerythritol diphosphates.The characteristics of high heat conductive insulating copolyamide composite has high thermal conductivity coefficient, high tensile, high fluidity, low water absorption and good insulation preformance, can be applied to electric, LED, automobile and other industries field.
Description
Technical field
The present invention relates to Material Field, more particularly to a kind of high heat conductive insulating copolyamide composite and its preparation side
Method.
Background technology
With the fast development of circuit board large scale integration and micro-packaging technology, electronic component volume constantly reduces,
Packing density more and more higher, and power is constantly increasing, caloric value also increases therewith.Therefore, radiating turns into one in electronics industry
Individual major issue.Metal with excellent heat conductivity performance, ceramics and carbon material, because electrical insulating property, machine-shaping property are poor,
It is relatively costly, it is difficult to the need for adapting to present technology development.Macromolecular material has light weight, insulation, corrosion-resistant, processing characteristics excellent
The big advantage of good, design freedom, but heat conductivility is poor.With macromolecular material as matrix, conduction powder is filled, by high score
Sub- material traditional molding methods, can obtain heat conductive insulating composite.Meanwhile, the heat conductive insulating composite also has corrosion-resistant
Property and preferable mechanical property, the heat exchanger material that can be used in Industrial Wastewater Treatment and Chemical Manufacture and powerful
The application fields such as the heat radiation lamp cup of LED.
Heat resistant polyamide is typically by aliphatic diamines and aromatic diacid, or aromatic diamines and fat
The diacid of race is prepared through polycondensation.Due to introducing phenyl ring on molecular backbone, heat resistant polyamide not only maintains fat
Mechanical property that polyamide has is good, acid and alkali-resistance and the advantages of self lubricity, also overcome that its water absorption rate is high, dimensional stability not
Good shortcoming, it is mainly used in electric, LED, automobile and other industries.However, the thermal conductivity of heat resistant polyamide is smaller, from
And its application in some fields is limited, such as connector, motor, transformer, solenoid, wound around coil system, LED illumination
The application fields such as radiating.
For above-mentioned problem, some researchs are done in currently available technology to the heat conductivility for improving polyamide, for example
Chinese patent CN 102070899A disclose a kind of insulating heat-conductive polyamide compoiste material, by polyamide (PA) resin, polyphenylene sulfide
Ether (PPS) resin, heat filling, glass fibre, coupling agent, antioxidant, processing aid are prepared from；Chinese patent CN
105462241A discloses a kind of material for improving polyamide PA6 thermal conductivity of material and preparation method thereof；Chinese patent CN
105462252A discloses a kind of technical scheme and preparation method of short fine enhancing heat conductive insulating nylon 46 composite；China
Patent CN 105504793A disclose a kind of halogen-free flameproof High-heat-conductiviinsulation insulation material and preparation method thereof, and the material is by nylon 6
Resin, modified aluminas, zinc oxide, magnesium hydroxide, toughener, halogen-free flame retardants, zinc stearate, antioxidant and coupling agent system
Into.
The content of the invention
The present invention be directed to the deficiencies in the prior art, it is therefore an objective to provide a kind of with high thermal conductivity coefficient, high tensile, height
The high heat conductive insulating copolyamide composite of mobility, low water absorption and good insulation preformance, can be applied to electric, LED,
Automobile and other industries field.
To reach above-mentioned purpose, the present invention uses following scheme：
A kind of high heat conductive insulating copolyamide composite, the composite is prepared from by the raw material of following weight portion：
The intrinsic viscosity of the copolyamide resin is 0.7~1.0dL/g.
The aliphatic polyamide resin is nylon 46 resin (PA46), polyhexamethylene adipamide resin
(PA66) at least one in.
The coupling agent be gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-
Gamma-aminopropyl-triethoxy-silane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-ammonia third
Ylmethyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, aniline first
At least one in ethyl triethoxy silicane alkane.
Wherein in some embodiments, the high heat conductive insulating copolyamide composite, by the raw material of following weight portion
It is prepared from：
Wherein in some embodiments, the high heat conductive insulating copolyamide composite, further preferably by following heavy
The raw material for measuring part is prepared from：
Wherein in some embodiments, the intrinsic viscosity of the copolyamide resin is 0.75~0.95dL/g；The fat
Fat polyamide resin is polyhexamethylene adipamide resin (PA66), and its inherent viscosity is 1.22~1.84dL/g.
Wherein in some embodiments, the coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy
At least one in base silane；The boron nitride is shaped as sheet, and particle diameter is 5~150 μm；The particle diameter of the aluminum oxide is 5
~60 μm；The carborundum is shaped as crystal whisker-shaped, and diameter of whiskers is 0.05~2.5 μm, draw ratio >=20.
Wherein in some embodiments, the copolyamide resin is formed by monomer 1 and polyesteramide copolymerization, the monomer
1 is that mol ratio is 1：0.9~0.99：0.01~0.1 decamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid, and it is described to benzene two
Both formic acid and aliphatic dibasic acid consumption and be 1 with the mol ratio of the decamethylene diamine, the aliphatic dibasic acid be adipic acid,
At least one in decanedioic acid, dodecanedioic acid, the polyesteramide addition is the 1~8% of the gross weight of the monomer 1.
Wherein in some embodiments, the copolyamide resin is obtained by following synthetic method：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while adding the polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, leads to 4~6min of nitrogen, so circulated 5~7 times,
Reactant is present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed of stirring-type polymer reactor is stated for 30~50r/min, wherein, when the stirring-type polymer reactor temperature reaches
At 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1~2 hour, normal pressure is deflated to, while being warming up to
After continuing to react 1~2 hour at 310~320 DEG C, after constant temperature persistently vacuumizes 0.3~1 hour, the copolyamide tree is obtained
Fat；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1~3% benzoic acid；The antioxygen
Agent is addition is the gross weight of the monomer 1 0.1~0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,
3- benzene diamides；Appropriate amount of water.
It is a further object of the present invention to provide the preparation method of high heat conductive insulating copolyamide composite.
The preparation method of above-mentioned high heat conductive insulating copolyamide composite, specific technical scheme is comprised the following steps：
(1) 4~12 are dried under conditions of the copolyamide resin and aliphatic polyamide resin being placed in into 80~100 DEG C
After hour, cooling, by copolyamide resin, aliphatic polyamide resin after cooling, and the toluene di-isocyanate(TDI), 2,
2'- (1,3- phenylenes)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides of N'- and double
(2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate is mixed in being added to homogenizer；
(2) coupling agent, boron nitride, aluminum oxide and carborundum are added in another homogenizer and are mixed
Close；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and in parallel pair of spiral shell
The mixture that lateral (such as the 4th area) addition step (2) of bar extruder (totally eight area) mix carries out melting extrusion, granulates,
Technological parameter is as follows：One area's temperature is 265~295 DEG C, and two area's temperature are 295~310 DEG C, and three area's temperature are 300~315 DEG C,
Four area's temperature are 305~315 DEG C, and five area's temperature are 305~315 DEG C, and six area's temperature are 305~315 DEG C, and seven area's temperature are 305
~315 DEG C, eight area's temperature are 305~315 DEG C, and die head temperature is 300~310 DEG C, and screw speed is 200~600rpm.
Wherein in some embodiments, by the copolyamide resin and aliphatic polyamide resin in the step (1)
Dried 4~6 hours under conditions of being placed in 90 DEG C；Technological parameter in the step (3) is：One area's temperature is 265~290 DEG C,
Two area's temperature are 295~305 DEG C, and three area's temperature are 300~310 DEG C, and four area's temperature are 305~310 DEG C, and five area's temperature are 305
~310 DEG C, six area's temperature are 305~310 DEG C, and seven area's temperature are 305~310 DEG C, and eight area's temperature are 305~310 DEG C, die head temperature
It is 300~305 DEG C to spend, and screw speed is 200~400rpm.
Wherein in some embodiments, the screw configuration of the parallel double-screw extruder is single thread；Spiro rod length L
It is 35~50 with the ratio between diameter D L/D；The screw rod be provided with more than 1 (containing 1) gear block area and more than 1 (containing 1)
Left-hand thread area.
Wherein in some embodiments, the ratio between described spiro rod length L and diameter D L/D are 35~45；The screw rod is provided with
2 gear block areas and 1 left-hand thread area.
Wherein in some embodiments, the copolyamide resin is formed by monomer 1 and polyesteramide copolymerization, the monomer
1 is that mol ratio is 1：0.9~0.99：0.01~0.1 decamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid, and it is described to benzene two
Both formic acid and aliphatic dibasic acid consumption and be 1 with the mol ratio of the decamethylene diamine, the aliphatic dibasic acid be adipic acid,
At least one in decanedioic acid, dodecanedioic acid, the polyesteramide addition is the 1~8% of the gross weight of the monomer 1.
Wherein in some embodiments, the copolyamide resin is obtained by following synthetic method：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while adding the polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, leads to 4~6min of nitrogen, so circulated 5~7 times,
Reactant is present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed of stirring-type polymer reactor is stated for 30~50r/min, wherein, when the stirring-type polymer reactor temperature reaches
At 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1~2 hour, normal pressure is deflated to, while being warming up to
After continuing to react 1~2 hour at 310~320 DEG C, after constant temperature persistently vacuumizes 0.3~1 hour, the copolyamide tree is obtained
Fat；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1~3% benzoic acid；The antioxygen
Agent is addition is the gross weight of the monomer 1 0.1~0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,
3- benzene diamides；Appropriate amount of water.
Principle of the invention is as follows：
In order to the thermal conductivity for solving current copolyamide resin is smaller and processing temperature narrow limits and processing characteristics not
Good defect, the present invention improves the heat conduction of copolyamide resin using the thermal conducting agent boron nitride, aluminum oxide and carborundum that compound
Performance, while improve the processing characteristics of copolyamide resin by aliphatic polyamide resin, because aliphatic polyamides
Polyimide resin possesses preferably mobile performance, and copolyamide resin possesses preferably mechanical property.And, fatty polyamide
The end group of resin and copolyamide resin can respectively with toluene di-isocyanate(TDI) isocyanate groups, 2,2'- (1,3- Asia benzene
Base) the oxazoline group of-bisoxazoline reacts, and improves the compatibility of both polyamides.Also, toluene diisocyanate
The isocyanate groups of acid esters, the oxazoline group of 2,2'- (1,3- phenylenes)-bisoxazoline can also be with boron nitride, oxidations
Coupling agent on aluminium, carborundum is reacted, so as to improve boron nitride, aluminum oxide, carborundum and above two polyamide
Interface binding power and compatibility, reduce their influences to polyamide compoiste material mechanical property.
The coupling agent that the present invention is used, preferably gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
Contain amino, above-mentioned auxiliary agent can react with the end group of above two polyamide, so as to further improve nitrogen
Change the interface binding power and compatibility of boron, aluminum oxide, carborundum and above two polyamide, reduce them multiple to polyamide
The influence of condensation material mechanical property.
The present invention improves the heat conductivility of copolyamide resin by compounding use boron nitride, aluminum oxide, carborundum, its
Synergy is obvious.Wherein, the boron nitride hardness of sheet is low, matter is soft, is susceptible to deform and contact with each other in Blending Processes,
So as to form the network structure of mutual overlap joint, more phonon routes of transmission are created, improve the thermal conductivity of polyamide compoiste material
Energy；Aluminum oxide has the characteristics of hardness is high, elevated temperature strength is big, antioxygenic property is good, and cheap, can effectively improve poly-
The heat conductivility of acid amides composite；The carborundum draw ratio of crystal whisker-shaped is big, thermal conductivity is high, good insulation preformance, can rise well
To bridge joint effect, dose advantageously form heat conduction network on a small quantity.
The fusing point of double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N, N'- is 272 DEG C, boiling point is more than
360 DEG C, the better heat stability in polyamide resin composite material Blending Processes, its amide group can be poly- with above two
The end group of amide resin reacts to improve compatibility, and hindered piperidine base can provide antioxidation and improve the dyeing of copolymer
Property.
The fusing point of double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates is 239 DEG C, heat decomposition temperature surpasses
350 DEG C are crossed, with good heat resistance and hydrolytic resistance, can be to provide superior in polyamide resin composite material Blending Processes
Colour stability and melt stability, while thermal degradation of the above two polyamide in pyroprocess can be prevented, and
The hot oxygen caused due to long-time is inhibited to change colour, it also offers in nitrogen oxides (NOx) color in the environment of gas
Stability, prevents gas from smoking discoloration.
Compared with prior art, the invention has the advantages that：
The present invention for current copolyamide resin thermal conductivity is smaller and processing temperature narrow limits and processing characteristics
Not good problem, the heat conductivility of copolyamide resin is improved by compounding using boron nitride, aluminum oxide, carborundum, and
Improve the processing characteristics of copolyamide resin using aliphatic polyamide resin, while using toluene di-isocyanate(TDI) and 2,
2'- (1,3- phenylene)-bisoxazoline is used as the compatilizer between both polyamides, and poly- as above two
Amide resin and the boron nitride of coupling agent, the compatilizer between aluminum oxide, carborundum are attached with, and compounding use N, N'- are double
(2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzenedicarboxamides and double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythrites
Bisphosphate processes the xanthochromia problem in Blending Processes, and preparation-obtained high heat conductive insulating copolyamide composite has
The characteristics of high thermal conductivity coefficient, high tensile, high fluidity, low water absorption and good insulation preformance, can be applied to it is electric,
LED, automobile and other industries field.
Brief description of the drawings
Fig. 1 show the preparation technology flow chart of high heat conductive insulating copolyamide composite of the present invention.
Specific embodiment
It is specific purposes, the function that can further appreciate that feature of the invention, technological means and reached, parses this hair
Bright advantage and spirit, by following examples, the present invention is further elaborated.
The reaction mechanism of high heat conductive insulating copolyamide composite of the present invention is following, and (preparation technology flow chart is see figure
1)：
Reaction mechanism
From above-mentioned reaction equation, the Amino End Group of aliphatic polyamide resin and copolyamide resin can be different with toluene two
The isocyanate groups of cyanate react, and the Amino End Group of aliphatic polyamide resin and copolyamide resin, end carboxyl can
Reacted with the oxazoline group with 2,2'- (1,3- phenylene)-bisoxazoline, such that it is able to increase both polyamide resins
Compatibility between fat.
The raw material that the embodiment of the present invention is used is as follows：
Copolyamide resin, self-control, the decamethylene diamine in raw material is selected from Wuxi Yinda Nylon Co., Ltd., terephthalic acid (TPA) choosing
From Beijing Yanshan Petrochemical Co., adipic acid, decanedioic acid, dodecanedioic acid are selected from Shandong Guang Yin new materials Co., Ltd,
Remaining auxiliary agent is selected from Chemical Reagent Co., Ltd., Sinopharm Group；
Polyhexamethylene adipamide resin (PA66), selected from China Shenma Group Co., Ltd., its inherent viscosity is respectively
1.22dL/g、1.66dL/g、1.84dL/g；
Toluene di-isocyanate(TDI), selected from Chemical Reagent Co., Ltd., Sinopharm Group；
2,2'- (1,3- phenylene)-bisoxazolines, selected from Chemical Reagent Co., Ltd., Sinopharm Group；
Coupling agent (gamma-aminopropyl-triethoxy-silane), selected from Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei；
Coupling agent (γ-aminopropyltrimethoxysilane), selected from Zhejiang boiling point Chemical Co., Ltd.；
Boron nitride, sheet, particle diameter is 5~150 μm, abundant up to special cermacis Co., Ltd selected from Shandong Zibo；
Aluminum oxide, particle diameter is 5~60 μm, selected from Zibo Nuo Da Chemical Co., Ltd.s；
Carborundum, crystal whisker-shaped, diameter of whiskers is 0.05~2.5 μm, draw ratio >=20, selected from Xuzhou victory innovative material science and technology
Co., Ltd；
Double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzenedicarboxamides of N, N'-, have selected from such as Dong Jinkangtai chemistry
Limit company；
Double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates, it is limited selected from Shanghai point credit fine chemistry industry
Company.
The present invention is described in detail below in conjunction with specific embodiment.
Copolyamide resin in following examples is formed by monomer 1 and polyesteramide copolymerization, and the monomer 1 is mol ratio
It is 1：0.9~0.99：0.01~0.1 decamethylene diamine, terephthalic acid (TPA), aliphatic dibasic acid, and the terephthalic acid (TPA) and fat
Both fat race binary acid consumptions and be 1 with the mol ratio of the decamethylene diamine, the aliphatic dibasic acid be adipic acid, decanedioic acid,
At least one in dodecanedioic acid, the polyesteramide addition is the 1~8% of the gross weight of the monomer 1, above-mentioned copolymerization acyl
Polyimide resin has such as following formula I structure：
In Formulas I, a=10~100, b=10~200, c=10~100, d=10~100, e=4 or 8 or 10, R are polyester
Acid amides, it has such as Formula Il structure：
In Formula II, x=10~200, y=10~200, z=10~100.
The synthetic method of copolyamide resin is as follows：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while adding the polyester acyl
Amine, and molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, leads to 4~6min of nitrogen, so circulated 5~7 times,
Reactant is present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, adjust institute
The mixing speed of stirring-type polymer reactor is stated for 30~50r/min, wherein, when the stirring-type polymer reactor temperature reaches
At 215 DEG C, 2.0MPa is deflated to, and maintains pressure in 2.0MPa, after reacting 1~2 hour, normal pressure is deflated to, while being warming up to
After continuing to react 1~2 hour at 310~320 DEG C, after constant temperature persistently vacuumizes 0.3~1 hour, the copolyamide tree is obtained
Fat；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1~3% benzoic acid；The antioxygen
Agent is addition is the gross weight of the monomer 1 0.1~0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,
3- benzene diamides；Appropriate amount of water.
Embodiment 1
Copolyamide resin used in the present embodiment is polyamide 10T/106 resins (PA10T/106), its raw material structure
Into and synthesis step it is as follows：
(1) by the monomer 1 after vacuum drying：1mol decamethylene diamines, 0.95mol terephthalic acid (TPA)s, 0.05mol adipic acids are added
To in stirring-type polymer reactor, while adding the 4% of monomer 1 gross weight polyesteramide, 1.5% benzoic acid, 0.2%
N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, add 100mL water as mass-and heat-transfer medium；
Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times makes in the environment that reactant is present under nitrogen protection, and control is stirred
It is 0.3MPa to mix system pressure in formula polymer reactor；
(2) in 3 hours by the closed constant-speed heating of stirring-type polymer reactor to 275 DEG C, adjust stirring-type polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to, and
Maintain pressure in 2.0MPa, after reacting 1.5 hours, be deflated to normal pressure, while after continuing to react 1.5 hours at being warming up to 315 DEG C,
After constant temperature persistently vacuumizes 0.5 hour, the copolyamide resin is obtained；
The intrinsic viscosity of the above-mentioned copolyamide resin (PA10T/106) for preparing is 0.85dL/g, melt temperature is
301℃。
A kind of high heat conductive insulating copolyamide composite of the present embodiment, is prepared from by the raw material of following weight portion：
The preparation method of above-mentioned high heat conductive insulating copolyamide composite, comprises the following steps：
(1) it is cold after being dried 5 hours under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in into 90 DEG C
But, by the copolyamide resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- Asias
Phenyl)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) coupling agent (γ-aminopropyltrimethoxysilane), boron nitride, aluminum oxide and carborundum are added to another
Mixed in homogenizer；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and in parallel pair of spiral shell
The mixture that lateral (the 4th area) addition step (2) of bar extruder (totally eight area) mix carries out melting extrusion, granulates, technique
Parameter is as follows：One area's temperature is 295 DEG C, and two area's temperature are 310 DEG C, and three area's temperature are 315 DEG C, and four area's temperature are 315 DEG C, 5th area
Temperature is 315 DEG C, and six area's temperature are 315 DEG C, and seven area's temperature are 315 DEG C, and eight area's temperature are 315 DEG C, and die head temperature is 310 DEG C,
Screw speed is 600rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 35,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 2
Copolyamide resin used in the present embodiment is polyamide 10T/1012 resins (PA10T/1012), its raw material
Constitute and synthesis step is as follows：
(1) by the monomer 1 after vacuum drying：1mol decamethylene diamines, 0.95mol terephthalic acid (TPA)s, 0.05mol dodecanedioic acids
Be added in stirring-type polymer reactor, at the same add the gross weight of monomer 1 4% polyesteramide, 1.5% benzoic acid,
0.2% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, addition 100mL water are used as mass-and heat-transfer
Medium；Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times, the environment for making reactant be present under nitrogen protection
In, it is 0.3MPa to control system pressure in stirring-type polymer reactor；
(2) in 3 hours by the closed constant-speed heating of stirring-type polymer reactor to 275 DEG C, adjust stirring-type polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to, and
Maintain pressure in 2.0MPa, after reacting 1.5 hours, be deflated to normal pressure, while after continuing to react 1.5 hours at being warming up to 315 DEG C,
After constant temperature persistently vacuumizes 0.5 hour, the copolyamide resin is obtained；
The intrinsic viscosity of the above-mentioned copolyamide resin (PA10T/1012) for preparing is 0.88dL/g, melt temperature is
297℃。
A kind of high heat conductive insulating copolyamide composite of the present embodiment, is prepared from by the raw material of following weight portion：
The preparation method of above-mentioned high heat conductive insulating copolyamide composite, comprises the following steps：
(1) it is cold after being dried 5 hours under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in into 90 DEG C
But, by the copolyamide resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- Asias
Phenyl)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminum oxide and carborundum are added to another
Mixed in homogenizer；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and in parallel pair of spiral shell
The mixture that lateral (the 4th area) addition step (2) of bar extruder (totally eight area) mix carries out melting extrusion, granulates, technique
Parameter is as follows：One area's temperature is 265 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 200rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 3
Copolyamide resin used in the present embodiment is polyamide 10T/1010 resins (PA10T/1010), its raw material
Constitute and synthesis step is as follows：
(1) by the monomer 1 after vacuum drying：1mol decamethylene diamines, 0.95mol terephthalic acid (TPA)s, 0.05mol decanedioic acid are added
To in stirring-type polymer reactor, while adding the 4% of monomer 1 gross weight polyesteramide, 1.5% benzoic acid, 0.2%
N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene diamides, add 100mL water as mass-and heat-transfer medium；
Then 5min is vacuumized, leads to nitrogen 5min, so circulation 6 times makes in the environment that reactant is present under nitrogen protection, and control is stirred
It is 0.3MPa to mix system pressure in formula polymer reactor；
(2) in 3 hours by the closed constant-speed heating of stirring-type polymer reactor to 275 DEG C, adjust stirring-type polymerisation
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, 2.0MPa is deflated to, and
Maintain pressure in 2.0MPa, after reacting 1.5 hours, be deflated to normal pressure, while after continuing to react 1.5 hours at being warming up to 315 DEG C,
After constant temperature persistently vacuumizes 0.5 hour, the copolyamide resin is obtained；
The intrinsic viscosity of the above-mentioned copolyamide resin (PA10T/1010) for preparing is 0.86dL/g, melt temperature is
299℃。
A kind of high heat conductive insulating copolyamide composite of the present embodiment, is prepared from by the raw material of following weight portion：
The preparation method of above-mentioned high heat conductive insulating copolyamide composite, comprises the following steps：
(1) it is cold after being dried 5 hours under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in into 90 DEG C
But, by the copolyamide resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- Asias
Phenyl)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminum oxide and carborundum are added to another
Mixed in homogenizer；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and in parallel pair of spiral shell
The mixture that lateral (the 4th area) addition step (2) of bar extruder (totally eight area) mix carries out melting extrusion, granulates, technique
Parameter is as follows：One area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 DEG C,
Screw speed is 400rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 45,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 4
The raw material of the copolyamide resin used in the present embodiment is constituted and synthesis step is with embodiment 3.
A kind of high heat conductive insulating copolyamide composite of the present embodiment, is prepared from by the raw material of following weight portion：
The preparation method of above-mentioned high heat conductive insulating copolyamide composite, comprises the following steps：
(1) it is cold after being dried 5 hours under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in into 90 DEG C
But, by the copolyamide resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- Asias
Phenyl)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminum oxide and carborundum are added to another
Mixed in homogenizer；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and in parallel pair of spiral shell
The mixture that lateral (the 4th area) addition step (2) of bar extruder (totally eight area) mix carries out melting extrusion, granulates, technique
Parameter is as follows：One area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 5
The raw material of the copolyamide resin used in the present embodiment is constituted and synthesis step is with embodiment 3.
A kind of high heat conductive insulating copolyamide composite of the present embodiment, is prepared from by the raw material of following weight portion：
The preparation method of above-mentioned high heat conductive insulating copolyamide composite, comprises the following steps：
(1) it is cold after being dried 5 hours under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in into 90 DEG C
But, by the copolyamide resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- Asias
Phenyl)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminum oxide and carborundum are added to another
Mixed in homogenizer；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and in parallel pair of spiral shell
The mixture that lateral (the 4th area) addition step (2) of bar extruder (totally eight area) mix carries out melting extrusion, granulates, technique
Parameter is as follows：One area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 6
The raw material of the copolyamide resin used in the present embodiment is constituted and synthesis step is with embodiment 3.
A kind of high heat conductive insulating copolyamide composite of the present embodiment, is prepared from by the raw material of following weight portion：
The preparation method of above-mentioned high heat conductive insulating copolyamide composite, comprises the following steps：
(1) it is cold after being dried 5 hours under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in into 90 DEG C
But, by the copolyamide resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- Asias
Phenyl)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminum oxide and carborundum are added to another
Mixed in homogenizer；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and in parallel pair of spiral shell
The mixture that lateral (the 4th area) addition step (2) of bar extruder (totally eight area) mix carries out melting extrusion, granulates, technique
Parameter is as follows：One area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 1
The raw material of the copolyamide resin used in this comparative example is constituted and synthesis step is with embodiment 3.
A kind of high heat conductive insulating copolyamide composite of this comparative example, is prepared from by the raw material of following weight portion：
The preparation method of above-mentioned high heat conductive insulating copolyamide composite, comprises the following steps：
(1) after being dried 5 hours under conditions of copolyamide resin being placed in into 90 DEG C, cooling, by the copolyamide after cooling
Resin, and double (2,2,6,6- tetramethyl -4- piperidyls) -1, the 3- benzenedicarboxamides of N, N'- and double (2,6- di-t-butyl -4-
Aminomethyl phenyl) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminum oxide and carborundum are added to another
Mixed in homogenizer；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and in parallel pair of spiral shell
The mixture that lateral (the 4th area) addition step (2) of bar extruder (totally eight area) mix carries out melting extrusion, granulates, technique
Parameter is as follows：One area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 2
The raw material of the copolyamide resin used in this comparative example is constituted and synthesis step is with embodiment 3.
A kind of high heat conductive insulating copolyamide composite of this comparative example, is prepared from by the raw material of following weight portion：
The preparation method of above-mentioned high heat conductive insulating copolyamide composite, comprises the following steps：
(1) it is cold after being dried 5 hours under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in into 90 DEG C
But, by double (2,2,6, the 6- tetramethyl -4- piperazines of the copolyamide resin after cooling, polyhexamethylene adipamide resin, and N, N'-
Piperidinyl) -1,3- benzenedicarboxamides and double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates are added to high-speed stirring
Mix and mixed in machine；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminum oxide and carborundum are added to another
Mixed in homogenizer；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and in parallel pair of spiral shell
The mixture that lateral (the 4th area) addition step (2) of bar extruder (totally eight area) mix carries out melting extrusion, granulates, technique
Parameter is as follows：One area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 3
The raw material of the copolyamide resin used in this comparative example is constituted and synthesis step is with embodiment 3.
A kind of high heat conductive insulating copolyamide composite of this comparative example, is prepared from by the raw material of following weight portion：
The preparation method of above-mentioned high heat conductive insulating copolyamide composite, comprises the following steps：
(1) it is cold after being dried 5 hours under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in into 90 DEG C
But, by the copolyamide resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- Asias
Phenyl)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) boron nitride, aluminum oxide and carborundum are added in another homogenizer and are mixed；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and in parallel pair of spiral shell
The mixture that lateral (the 4th area) addition step (2) of bar extruder (totally eight area) mix carries out melting extrusion, granulates, technique
Parameter is as follows：One area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 40,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 4
The raw material of the copolyamide resin used in this comparative example is constituted and synthesis step is with embodiment 3.
A kind of high heat conductive insulating copolyamide composite of this comparative example, is prepared from by the raw material of following weight portion：
The preparation method of above-mentioned high heat conductive insulating copolyamide composite, comprises the following steps：
(1) it is cold after being dried 5 hours under conditions of copolyamide resin and polyhexamethylene adipamide resin being placed in into 90 DEG C
But, by the copolyamide resin after cooling, polyhexamethylene adipamide resin, and toluene di-isocyanate(TDI), 2,2'- (1,3- Asias
Phenyl)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and double (tertiary fourths of 2,6- bis-
Base -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) coupling agent (gamma-aminopropyl-triethoxy-silane), boron nitride, aluminum oxide and carborundum are added to another
Mixed in homogenizer；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and in parallel pair of spiral shell
The mixture that lateral (the 4th area) addition step (2) of bar extruder (totally eight area) mix carries out melting extrusion, granulates, technique
Parameter is as follows：One area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of the parallel double-screw extruder is double thread, and the ratio between spiro rod length L and diameter D L/D are 30,
The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
It is below embodiment and comparative example list (table 1)：
The embodiment of table 1 constitutes weight portion list with comparative example raw material
Double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of the N of above example and comparative example, N'- and
Double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates are respectively 0.15 part, 0.15 part.
The various embodiments described above and the made working of plastics sample of comparative example are carried out into following performance test (result is as shown in table 2)：
Parallel thermal conductivity in face：By ASTM E1461 standard testings；
Tensile property：By GB/T 1040.1-2006 standard testings, rate of extension 10mm/min；
Mobile performance：By GB/T 3682-2000 standard testings, 309 DEG C of test temperature, load 1.2kg；
Water absorbing properties：By GB/T 1034-2008 standard testings, testing time 24h；
Surface resistivity：By the standard testings of IEC 60093.
The embodiment of table 2 and comparative example performance list
As can be seen that the addition of boron nitride, aluminum oxide and carborundum is more from embodiment 1~6, copolyamide resin
Parallel thermal conductivity and tensile strength are bigger in the face of composite；Aliphatic polyamide resin (polyhexamethylene adipamide resin)
Addition it is more, the melt index of copolyamide resin composite materials is bigger, and processing characteristics is better；The water absorption rate of each embodiment
It is little with surface resistivity change.In summary factor, the combination property of embodiment 6 is optimal.
It is compared with embodiment 6, comparative example 1 is to be not added with aliphatic polyamide resin (polyhexamethylene adipamide resin)
Copolyamide resin composite materials, its melt index is only 6g/10min (309 DEG C of test temperature, load 1.2kg), processability
Can not be good；Comparative example 2 is to be not added with toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylenes)-bisoxazoline (PBO) to be total to
Polyamide resin composite material, polyamide compatibility is not together for aliphatic polyamide resin (polyhexamethylene adipamide resin)
It is good, so as to the tensile property thermal conductivity parallel with face to copolyamide resin composite materials causes bad influence；Contrast
Example 3 is the copolyamide resin composite materials for being not added with coupling agent, boron nitride, aluminum oxide and carborundum and above two polyamide
Resin compatible is not good, bad so as to be caused to the tensile property thermal conductivity parallel with face of copolyamide resin composite materials
Influence；The screw configuration of the parallel double-screw extruder of comparative example 4 is double thread, the ratio between spiro rod length L and diameter D L/D
It is 30, and the screw configuration of the parallel double-screw extruder of embodiment 6 is single thread, the ratio between spiro rod length L and diameter D L/D
It is 40, by contrast it can be found that using the Screw Parameters of the parallel double-screw extruder described in embodiment 6, it is prepared
Copolyamide resin composite materials face in parallel thermal conductivity, tensile property, processing characteristics be greatly improved, obtain height and lead
The high heat conductive insulating copolyamide composite of hot coefficient, high tensile, high fluidity, low water absorption and good insulation preformance
Beneficial effect.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of high heat conductive insulating copolyamide composite, it is characterised in that be prepared from by the raw material of following weight portion：
The intrinsic viscosity of the copolyamide resin is 0.7~1.0dL/g；
The aliphatic polyamide resin is at least one in nylon 46 resin, polyhexamethylene adipamide resin；
The coupling agent be gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-
Aminopropyl triethoxysilane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl
Methyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl
At least one in triethoxysilane.
2. high heat conductive insulating copolyamide composite according to claim 1, it is characterised in that by following weight portion
Raw material is prepared from：
3. high heat conductive insulating copolyamide composite according to claim 1 and 2, it is characterised in that the copolymerization acyl
The intrinsic viscosity of polyimide resin is 0.75~0.95dL/g；The aliphatic polyamide resin is polyhexamethylene adipamide resin, its
Inherent viscosity is 1.22~1.84dL/g.
4. high heat conductive insulating copolyamide composite according to claim 1 and 2, it is characterised in that the coupling agent
It is at least one in gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane；The boron nitride is shaped as
Sheet, particle diameter is 5~150 μm；The particle diameter of the aluminum oxide is 5~60 μm；The carborundum is shaped as crystal whisker-shaped, and whisker is straight
Footpath is 0.05~2.5 μm, draw ratio >=20.
5. high heat conductive insulating copolyamide composite according to claim 1 and 2, it is characterised in that the copolymerization acyl
Polyimide resin is formed by monomer 1 and polyesteramide copolymerization, and the monomer 1 is that mol ratio is 1：0.9~0.99：0.01~0.1 last of the ten Heavenly stems
Diamines, terephthalic acid (TPA), aliphatic dibasic acid, and both the terephthalic acid (TPA) and aliphatic dibasic acid consumption and with the last of the ten Heavenly stems
The mol ratio of diamines is 1, and the aliphatic dibasic acid is at least one in adipic acid, decanedioic acid, dodecanedioic acid, described poly-
Esteramides addition is the 1~8% of the gross weight of the monomer 1.
6. high heat conductive insulating copolyamide composite according to claim 5, it is characterised in that the copolyamide tree
Fat is obtained by following synthetic method：
(1) by vacuum drying after the monomer 1 be added in stirring-type polymer reactor, while add the polyesteramide,
And molecular weight regulator, antioxidant, water；Then 4~6min is vacuumized, leads to 4~6min of nitrogen, so circulated 5~7 times, made
Reactant is present in the lower environment of nitrogen protection, control in the stirring-type polymer reactor system pressure for 0.2~
0.3MPa；
(2) in 2~4 hours by the closed constant-speed heating of stirring-type polymer reactor to 272~280 DEG C, regulation described in stir
The mixing speed of formula polymer reactor is mixed for 30~50r/min, wherein, when the stirring-type polymer reactor temperature reaches 215
DEG C when, be deflated to 2.0MPa, and maintain pressure in 2.0MPa, after reaction 1~2 hour, normal pressure is deflated to, while being warming up to 310
After continuing to react 1~2 hour at~320 DEG C, after constant temperature persistently vacuumizes 0.3~1 hour, the copolyamide resin is obtained；
The molecular weight regulator is addition is the gross weight of the monomer 1 0.1~3% benzoic acid；The antioxidant is
Addition is the N of the 0.1~0.3% of the gross weight of the monomer 1, N'- bis- (2,2,6,6- tetramethyl -4- piperidyls) -1,3- benzene
Diamides；Appropriate amount of water.
7. a kind of preparation method of the high heat conductive insulating copolyamide composite described in any one of claim 1-6, its feature
It is to comprise the following steps：
(1) dried 4~12 hours under conditions of the copolyamide resin and aliphatic polyamide resin being placed in into 80~100 DEG C
Afterwards, cool down, by copolyamide resin, aliphatic polyamide resin after cooling, and the toluene di-isocyanate(TDI), 2,2'-
(1,3- phenylenes)-bisoxazoline, N, double (2,2,6,6- tetramethyl -4- the piperidyls) -1,3- benzenedicarboxamides of N'- and it is double (2,
6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate mixed in being added to homogenizer；
(2) coupling agent, boron nitride, aluminum oxide and carborundum are added in another homogenizer and are mixed；
(3) during the compound for mixing step (1) is through feeder addition parallel double-screw extruder, and squeezed in parallel double-screw
Going out the mixture that the lateral addition step (2) of machine mixes carries out melting extrusion, granulates, and technological parameter is as follows：One area's temperature is
265~295 DEG C, two area's temperature are 295~310 DEG C, and three area's temperature are 300~315 DEG C, and four area's temperature are 305~315 DEG C, five
Area's temperature be 305~315 DEG C, six area's temperature be 305~315 DEG C, seven area's temperature be 305~315 DEG C, eight area's temperature be 305~
315 DEG C, die head temperature is 300~310 DEG C, and screw speed is 200~600rpm.
8. preparation method according to claim 7, it is characterised in that by the copolyamide resin in the step (1)
Dried 4~6 hours under conditions of being placed in 90 DEG C with aliphatic polyamide resin；Technological parameter in the step (3) is：One area
Temperature is 265~290 DEG C, and two area's temperature are 295~305 DEG C, and three area's temperature are 300~310 DEG C, and four area's temperature are 305~310
DEG C, five area's temperature are 305~310 DEG C, and six area's temperature are 305~310 DEG C, and seven area's temperature are 305~310 DEG C, and eight area's temperature are
305~310 DEG C, die head temperature is 300~305 DEG C, and screw speed is 200~400rpm.
9. the preparation method according to claim 7 or 8, it is characterised in that the screw shaped of the parallel double-screw extruder
Shape is single thread；The ratio between spiro rod length L and diameter D L/D are 35~50；The screw rod is provided with the gear block area of more than 1
Left-hand thread area with more than 1.
10. preparation method according to claim 9, it is characterised in that the ratio between described spiro rod length L and diameter D L/D are 35
~45；The screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710014341.8A CN106832916B (en) | 2017-01-09 | 2017-01-09 | High heat conductive insulating copolyamide composite material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710014341.8A CN106832916B (en) | 2017-01-09 | 2017-01-09 | High heat conductive insulating copolyamide composite material and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106832916A true CN106832916A (en) | 2017-06-13 |
| CN106832916B CN106832916B (en) | 2019-02-12 |
Family
ID=59117919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710014341.8A Active CN106832916B (en) | 2017-01-09 | 2017-01-09 | High heat conductive insulating copolyamide composite material and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106832916B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129834A (en) * | 2017-12-28 | 2018-06-08 | 许飞扬 | A kind of flame-resistant insulation composite nylon material |
| CN111334042A (en) * | 2020-04-14 | 2020-06-26 | 广东圆融新材料有限公司 | Low-dielectric-constant polyphenylene sulfide composition and preparation method thereof |
| CN111849164A (en) * | 2020-08-14 | 2020-10-30 | 广东圆融新材料有限公司 | Low-linear expansion coefficient polyphenylene sulfide/polyamide 66 composition and preparation method thereof |
| CN111875963A (en) * | 2020-08-18 | 2020-11-03 | 广东圆融新材料有限公司 | Low-linear expansion coefficient polyphenylene sulfide/nylon 6 composite material and preparation method thereof |
| CN111944308A (en) * | 2020-08-31 | 2020-11-17 | 广东圆融新材料有限公司 | Nylon 6 composite material with low linear expansion coefficient and preparation method thereof |
| CN111978719A (en) * | 2020-08-28 | 2020-11-24 | 广东圆融新材料有限公司 | Polyamide 66 composite material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0379663A (en) * | 1989-08-23 | 1991-04-04 | Teijin Ltd | Polyamide resin composition |
| CN102585491A (en) * | 2012-01-09 | 2012-07-18 | 金发科技股份有限公司 | Reinforced polyamide composition with high liquidity and low warpage and preparation method and application thereof |
| CN102719099A (en) * | 2012-06-08 | 2012-10-10 | 金发科技股份有限公司 | Thermal conductive molding compound and preparation method thereof |
| CN105295034A (en) * | 2015-12-07 | 2016-02-03 | 中北大学 | Biology-based semi-aromatic polyamide and synthesis method thereof |
| CN105295033A (en) * | 2015-12-07 | 2016-02-03 | 中北大学 | Long-carbon-chain semi-aromatic polyamide and synthetic method thereof |
| CN105295032A (en) * | 2015-12-07 | 2016-02-03 | 中北大学 | Long-carbon-chain semi-aromatic nylon and synthetic method thereof |
-
2017
- 2017-01-09 CN CN201710014341.8A patent/CN106832916B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0379663A (en) * | 1989-08-23 | 1991-04-04 | Teijin Ltd | Polyamide resin composition |
| CN102585491A (en) * | 2012-01-09 | 2012-07-18 | 金发科技股份有限公司 | Reinforced polyamide composition with high liquidity and low warpage and preparation method and application thereof |
| CN102719099A (en) * | 2012-06-08 | 2012-10-10 | 金发科技股份有限公司 | Thermal conductive molding compound and preparation method thereof |
| CN105295034A (en) * | 2015-12-07 | 2016-02-03 | 中北大学 | Biology-based semi-aromatic polyamide and synthesis method thereof |
| CN105295033A (en) * | 2015-12-07 | 2016-02-03 | 中北大学 | Long-carbon-chain semi-aromatic polyamide and synthetic method thereof |
| CN105295032A (en) * | 2015-12-07 | 2016-02-03 | 中北大学 | Long-carbon-chain semi-aromatic nylon and synthetic method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 汪朝阳 等: "扩链反应在高分子材料合成中的应用", 《化学推进剂与高分子材料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129834A (en) * | 2017-12-28 | 2018-06-08 | 许飞扬 | A kind of flame-resistant insulation composite nylon material |
| CN111334042A (en) * | 2020-04-14 | 2020-06-26 | 广东圆融新材料有限公司 | Low-dielectric-constant polyphenylene sulfide composition and preparation method thereof |
| CN111849164A (en) * | 2020-08-14 | 2020-10-30 | 广东圆融新材料有限公司 | Low-linear expansion coefficient polyphenylene sulfide/polyamide 66 composition and preparation method thereof |
| CN111875963A (en) * | 2020-08-18 | 2020-11-03 | 广东圆融新材料有限公司 | Low-linear expansion coefficient polyphenylene sulfide/nylon 6 composite material and preparation method thereof |
| CN111978719A (en) * | 2020-08-28 | 2020-11-24 | 广东圆融新材料有限公司 | Polyamide 66 composite material and preparation method thereof |
| CN111944308A (en) * | 2020-08-31 | 2020-11-17 | 广东圆融新材料有限公司 | Nylon 6 composite material with low linear expansion coefficient and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106832916B (en) | 2019-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106832916B (en) | High heat conductive insulating copolyamide composite material and preparation method | |
| CN106519654B (en) | Halogen-free fire-retarding reinforced polyamide composite material and preparation method | |
| CN106479174B (en) | Fire-retardant enhancing copolyamide 6T composite material and preparation method | |
| CN106497043B (en) | Fire-retardant enhancing copolyamide composite material and preparation method | |
| CN106832915B (en) | High heat conductive insulating polyamide 6 T composite material and preparation method | |
| CN106519665B (en) | Flame retardancy reinforced polyamide composite material and preparation method thereof | |
| CN102203188A (en) | Thermoplastic composition including thermally conductive filler and hyperbranched polyesteramide | |
| CN109679341A (en) | A kind of high intensity, high glaze, apperance performance fiberglass reinforced high-temperature nylon material and preparation method thereof | |
| CN106751807B (en) | High heat conductive insulating copolyamide 6T composite material and preparation method | |
| CN106751800B (en) | Laser direct forming copolyamide 6T composite material and preparation method | |
| CN105504698A (en) | Heat-resistance liquid crystal polyester resin compound and preparation method thereof | |
| CN106433116B (en) | High temperature resistant copolyamide 6T composition and preparation method thereof | |
| CN107057341B (en) | High heat conductive insulating polyamide compoiste material and preparation method thereof | |
| JP5468975B2 (en) | High heat conductivity thermoplastic resin heat sink | |
| CN106366657B (en) | High heat resistance height flows nylon composite materials and preparation method thereof | |
| CN106398193B (en) | Heat resistant polyamide 6T/11 composition and preparation method thereof | |
| CN106675020B (en) | Laser direct forming polyamide 6 T composite material and preparation method | |
| CN106336653B (en) | High temperature resistant co-polyamide composition and preparation method thereof | |
| CN115260755B (en) | Polyamide composite material and preparation method and application thereof | |
| CN106633844B (en) | High heat resistance height flows copolyamide 6T composite material and preparation method | |
| CN106519652B (en) | High heat resistance height flows polyamide compoiste material and preparation method thereof | |
| JP3458544B2 (en) | Copolyamide and method for producing the same | |
| CN106675012B (en) | Laser direct forming polyamide compoiste material and preparation method thereof | |
| CN106519664B (en) | High heat resistance height flows copolyamide composite material and preparation method | |
| CN106433119B (en) | Heat resistant polyamide 10T/11 composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 523850 Baibugao Avenue, Wushajiang, Chang'an Town, Dongguan City, Guangdong Province, 355 Patentee after: Guangdong Sinoplast New Materials Co.,Ltd. Address before: 523850 Baibugao Avenue, Wushajiang, Chang'an Town, Dongguan City, Guangdong Province, 355 Patentee before: GUANGDONG SINOPLAST ADVANCED MATERIAL CO.,LTD. |